EP0466754B1 - Produit isolant en laine de fibre minerale, destine en particulier a l'isolation thermique de conduites et procede de preparation d'un tel produit - Google Patents
Produit isolant en laine de fibre minerale, destine en particulier a l'isolation thermique de conduites et procede de preparation d'un tel produit Download PDFInfo
- Publication number
- EP0466754B1 EP0466754B1 EP90905535A EP90905535A EP0466754B1 EP 0466754 B1 EP0466754 B1 EP 0466754B1 EP 90905535 A EP90905535 A EP 90905535A EP 90905535 A EP90905535 A EP 90905535A EP 0466754 B1 EP0466754 B1 EP 0466754B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- binder
- slag
- water glass
- product
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/645—Impregnation followed by a solidification process
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
Definitions
- the present invention relates to an insulating product of mineral fibres intended in particular for the heat insulation of pipes.
- the product shall have a good temperature resistance, moisture resistance and a strength that resists a high temporary load, e.g. the steps of the pipe fitter on the pipe during installation operations.
- the insulating product shall be shapeable at once or later to the desired shape and subsequently curable at the prevailing outer temperature or at a raised temperature.
- the production shall be feasible in a conventional installation for the production of mineral wool webs.
- the curing temperature shall be adaptabe to the circumstances and the curing time shall be short.
- the Finnish patent specification 67751 discloses the production of insulating bodies based on mineral wool.
- clay sludge preferably bentonite
- the process requires a curing of several hours in a furnace.
- the insulating body has a good temperature resistance, of at least 800 ° C, but is expensive owing to a slow and costly production process and expensive raw material.
- An additional drawback of the bentonite body is its coarse surface, requiring an additional surface treatment, i.e. milling, thus increasing the price of the material.
- Phenol cured insulating bodies are also known. Phenol is a fairly cheap and rapidly curing binder. A phenol cured product resists temperatures of up to 250 ° C, but if the temperature is above 250 ° C for a long period of time, the bonds are destroyed. At higher temperatures, of 400 ° C and more, the binder residues flare up, the temperature rises rapidly and the product collapses. Another drawback of phenol insulating bodies consists in their emitting poisonous gases during burning.
- the SE lay-out print 420 488 discloses the use of a mass based on water glass and clay mineral substances as a binding agent.
- the binder provides a good water and heat resistance in the product.
- the product has a poor compression resistance, meaning that e.g. a tubular bowl made of mineral fibres and treated according to the layout print does not resist temporary load. Moreover, the product is brittle and thus causes dusting.
- SU 614061 discloses an insulating product comprising at least 35 wt-% of perlite sand and optionally up to 20 wt-% of kaolin fibers (not mineral fibers) where the binder consists of synthetic AI-Ca-slag and water glass.
- DK-C-69522 relates to a stiff insulating material of mineral wool, e.g. slag wool, which is impregnated with water glass and subsequently heated so that the water glass is transformed to a foam whereafter the material is cooled.
- mineral wool e.g. slag wool
- GB-A-457 842 relates to an insulating product consisting e.g. of slag wool which is impregnated e.g. with an alkaline or potassium salt in such proportions that a silica gel is formed and a portion of the silicate remains free to combine separately with the slag wool.
- water glass does not act as an activator of slag.
- SU 622781 discloses a fire-resistant coating containing mainly mineral fiber (30-60 wt-%) and water glass (30-50 wt-%).
- US 2 904 444 is related to an insulating material of calcium hydroxide and diatomaceous earth.
- the material does not contain mineral wool nor is it treated with water glass.
- CH-A5-238299 relates to a coating agent containing water glass and slag wool (preferably in the proportion 3:1).
- an insulating product can be achieved, which is especially suitable as a tubular bowl, out of a mineral fibre web prepared in a conventional manner by using as a binding agent a water glass based binder with an addition of slag.
- the slag imparts many valuable properties to the insulating material.
- the alkalis of the water glass act as activators of the slag (cf. slag alkali cement). Together with water glass, slag forms a hydraulic bond giving the cured product an improved compression resistance, a reduced brittleness and thus reduced dusting and greater dust particles, compared to products treated with binders containing water glass without a slag addition.
- a good temperature resistance is achieved in a product containing a binder based on water glass and having a slag addition. Due to the hydraulic bond of the slag to the water glass, the water is firmly bound, chemically bound to the structure. The chemically bound water increases the fire-resistance capacity of the material in that the water evaporating at a fire temperature keeps down the temperature for a longer period.
- a water glass based binder resists a long-lasting temperature charge of up to 800 °C.
- the slag increases the crystallinity of the material, thus reducing the moisture absorption tendency and the moisture sensitivity.
- the curing time for a product containing water glass and slag in the binder and by using conventional curing in a curing chamber is approx. 20-60 s for thin products and approx. 20 min. at the most for thick tubular bowls. Equally good curing times are achieved with phenol containing binders, but these binders are unsuitable in other respects. Other known binders require curing times of up to several hours.
- Another advantage of the system water glass/slag is that the binder enables the forming of no-swelling compounds, although the temperature exceeds the swelling temperature of pure water glass, 160°C.
- the advantageous effects of slag are achieved with relatively small amounts of slag, both with regard to the amount of water glass and to the amount of fibres.
- the weight ratio of the dry substance of the water glass to the slag can be approx. 100:1 - 100:50, prefrably 10:1 - 10:2.
- the weight ratio of the mineral fibre amount to the dry substance of the water glass can be approx. 100:1 - 100:20, preferably 100:5 - 100:15.
- the slag of the binder is preferably blast furnace slag.
- the slag/water glass system is well controllable and thus provides a geat flexiblity for the method of preparing an insulating product of mineral wool.
- Controllable components are among others:
- the slag reacts with the alkalis of the water glass, i.e. it is activated.
- water resistant hydrate phases of a zeolite type are obtained.
- the molar ratio R s the ratio of the silicon moles to the alkali moles in the water glass
- R s the ratio of the silicon moles to the alkali moles in the water glass
- a higher alkali content, i.e. a lower molar ratio R s requires a higher slag portion in order to tie up the alkalis in a water resistant form.
- the main components of the slag-glass are CaO, MgO, Si0 2 , Al 2 O 3 . It is generally true about slag/water glass systems that the lower the CaO content, i.e. the ratio CaO/Si0 2 , the lower a molar ratio R s should be used in order to obtain a hydraulic bond within a reasonable period of time. When using low molar ratios, R s ⁇ 2.7, the slag content has to be increased. With a higher ratio CaO/SiO 2 1.3, water glass can be used with R s 3.3 , still obtaining a sufficient reactivity.
- the reaction degree is controlled by means of the temperature and the curing time. A higher curing temperature shortens the curing time and vice versa.
- a lower R s shortens the curing time at a constant temperature.
- a higher R s requires a longer curing time or a higher temperature.
- reaction degree and the curing rate can be further increased.
- a finished hydrate phase is consequently created, speeding up the curing when the binder has been applied onto the mineral wool.
- the slag content has to be increased in order to prevent the water glass from swelling (cf. slag alkali cement).
- Trituration of the slag increases the reaction rate and the reactivity. This enables to use a water glass with a higher R s , or optionally a very rapid curing can be ahieved at a lower R s .
- a finely ground slag also improves the stability of the slurry of water glass and slag.
- the water glass can be a sodium, potassium, lithium or ammonium silicate solution. In case the slag content is high, hydroxides and/or carbonates can be added.
- the preparation of a mineral wool product and the addition of the binder based on water glass and containing slag takes place conventionally in a conventional set of apparatus.
- the binder is added as a solution through a nozzle to the fibres in the wool chamber of a conventional machine line.
- the water glass and the slag are premixed in water and are kept in agitation before the distribution on the wool.
- the curing of the binder mixed wool material takes place at once or later, at room temperature or at a raised temperature.
- the binder solution can contain possible additional curing, modifying, dust binding and/or hydrophobing agents.
- the spraying of the binder solution and the additives takes place directly after the fibre formation, preferably in the wool chamber. This is an essential advantage, since the wool is in a virginal state here and thus has a good adhesiveness.
- the binder composition is sprayed on the wool through the binder nozzles of the centrifuge, both peripheral and central sprayers being then usable.
- two different solutions can be fed into the wool, so that possible modifying and/or additional curing agents are fed through the one sprayer and a slurry of water glass/slag + possible modifying agents through the other sprayer.
- An additional binder solution can appropriately be added to the wool in a subsequent step of the production of the insulating material.
- a composite having a better resistance is achieved.
- additional additives on the primary web special properties can be given to the material.
- the mixing can be carried out for istance by rapid mixing, e.g. in tubular mixers.
- the dwell time will be short enough not to allow any gelling or precipitating reactions to take place.
- the required additional water is also adjusted by feeding into the rapid mixer.
- the water amount is adjusted so as to provide the correct moisture for the primary web and prevent dusting.
- the water evaporation taking place in the wool chamber increases the viscosity of the fibre composition applied onto the fibre.
- the high viscosity means a very low ion migration, thus decreasing the reaction rate. In this manner, the primary web retains its elasticity and curability for several days/weeks, provided that further water discharge is prevented.
- the mineral fibre web is cured at room temperature, for instance between metal sheets.
- the sheet will acquire a better flexibility.
- a slowly cured fibre body is, as is known, more flexible, elastic, than a fibre body that has to be cured at a high temperature.
- a secondary web having the desired thickness is taken up in an uncured state and stored in a non curing environment, e.g. enclosed in plastic at a suitable temperature and during a determined time at the most.
- This insulating material is used in situ for the insulation in places that are not easily accessable and have an awkward shape, such as for instance renovation objects. Afterwards, the insulation cures at the prevailing temperature. It is relatively easy to apply an insulating mat having a suitable thickness onto or around various bodies difficult to access. The curing does not require any special measures or equipment since it takes place spontaneously at the prevailing temperature.
- the method is also suitable for blow wool applications, in which uncured fibre material torn into small tufts is applied onto pipes, where the wool can be cured at the prevailing temperature.
- a secondary web is shaped to the desired shape of a tubular bowl, and is subsequently cured in a known manner.
- the curing can take place rapdily at a high temperature or slower at a lower temperature.
- Additional additives like additional curing, modifying, dust binding and hydrophobizing agents cooperate with the water glass/slag system.
- the additional curing agents consist of mineral salts and compounds, suitable acids, esters or alcohols or of combinations of these.
- the mineral salts can be e.g. magnesium, aluminium or calcium salts or compounds.
- Phosphoric acid for instance, is a usable acid.
- Buffer curing agents can also be used for adjusting the storage time.
- the additional curing agent may be a combination of the above mentioned curing agents.
- modifying agents like organic and unorganic polymers, cellulose and silicones like silicon organic polymers are appropriately used. Also monomers polymerized by e.g. a pH change or a temperature rise during the curing can be used.
- the modifying agents of water glass have in common the fact of not being film forming. By means of the modifying agents one aims at softening the water glass, thus increasing its adhesiveness to the fibre surface.
- the water glass modifier improves the elastic properties, the water resistance, carbonation resistance etc. of the water glass.
- dust binding agents alcohols, polyols, film forming polymers, gelling polymers, waxes, oils, fats, paraffines etc. are appropriately used.
- the task of the dust binding agent is to bind together the dust or to bind it to the main matrice either physically (film forming) or chemically (surface active properties).
- melting dust binding agents e.g. stearates
- curing dust binders forming a film over the matrice.
- a great number of the dust binding agents simultaneously have a water repellent effect.
- hydrophobizing agent The task of the hydrophobizing agent is to prevent water and moisture from penetrating into the product.
- hydrophobizing agents silanes, silicones, oils, various hydrophobic compounds and hydrophobic starch are used. It is essential that possible hydrophilic emulgators are destroyable, which happens by raising the pH value or by a temperature raise.
- the polybutene silane compound has proved especially advantageous as a dust binding agent and a hydrophobing agent.
- the polybutene acts as a dust binder and the silane as a hydrophobing agent.
- compatible compounds can be mixed in advance, whereas non compatible compounds have to be mixed immediately before the application or applied through separate nozzles.
- a modifying solution dry content 8%
- the water glass forms 11.2% of the wool
- the slag 13% of the water glass
- the modifiers 1.8% of the water glass The wool production was 2.8 tons/h and the dosing of the various solutions was 10.2 I/min of water glass-slag- suspension, 3.2 I/min of modyfier solution as well as water 10 I/min.
- the primary web was rolled into a tubular bowl having a diametre of 350 mm and a wall thickness of 60 mm and the tubular bowl was cured at 145°C for 3 min.
- a piece 63.5 x 63.5 mm was cut out from the tubular bowl and was tested with regard to linear shrinking at 600 ° C according to ASTM 356-60. The shrinking was only 1.4% when the density of the product was 101 kg/m 3 .
- dry substance the water glass forms 11.4% of the wool, the slag 5%, the phosphoric acid 2.5% and the modifiers 0.8% of the water glass.
- the wool production was 3.2 tons/h and the dosing of the various solutions was 12.5 I/min of the water glass/slag-suspension, 5.3 I/min of the additional curer, 4.2 I/min of the modifier solution as well as water 11 I/min.
- a sheet web was prepared in a curing chamber at 140°C. Fire tests according to SFS 4193 were carried out on sheets having a thickness of only 26 mm and a density of 217 and 225 kg/m 3 respectively, yielding a fire resistance of 52 and 58 min. respectively.
- the temperature rise on the fire side according to SFS 4193 appears from fig. 1 and table 1. The test was continued for one hour and the temperature was 925 ° C at the end of the test.
- the sheet was totally undeformed and unbent and the burnt area still had a high residual strength.
- Fig. 2 shows a typical relation between the splitting resistance and the density of a sheet product according to the invention.
- Fig. 3 shows the relation between the tensile bending strength and the density of a number of sheet products according to the invention.
- the force required for compressing a cured sheet product according to the invention 5 and 10% respectively is indicated in fig.4.
- the force is given as kN/m 2 as a function of the density.
- a modifier solution dry content 10%
- the water glass represents 15.8% of the wool
- the wool production was 2.8 tons/h and the dosing of the various solutions was 13.2 I/min of water glass/slag-suspension, 6.0 I/min of modifier solution and water 8 I/min.
- tubular bowls were prepared, having an outer diametre of 520 mm, a thickness of 120 mm and a density of 96.0 kg/m 3 .
- the bowls were mounted on a steam pipe, whose temperature was raised up to 520 °C. After 60 hours at this temperature the insulation was inspected and its value was determined.
- the value was: 0.1010 W/m ° C at 520 °C.
- the bowls resisted the temperature (520 °C) well.
- the only remarkable difference was that the inner surface of the bowl had become harder than the outer surface, probably due to the continued curing of the binder.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Thermal Insulation (AREA)
- Nonwoven Fabrics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Steroid Compounds (AREA)
- Glass Compositions (AREA)
Claims (13)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI891659 | 1989-04-06 | ||
FI891659A FI891659A (fi) | 1989-04-06 | 1989-04-06 | Foerfarande foer framstaellning av en mineralullsprodukt med god temperaturtaolighet. |
PCT/FI1990/000093 WO1990012139A1 (fr) | 1989-04-06 | 1990-04-05 | Produit isolant en laine de fibre minerale, destine en particulier a l'isolation thermique de conduites et procede de preparation d'un tel produit |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0466754A1 EP0466754A1 (fr) | 1992-01-22 |
EP0466754B1 true EP0466754B1 (fr) | 1995-07-05 |
EP0466754B2 EP0466754B2 (fr) | 2000-01-19 |
Family
ID=8528194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90905535A Expired - Lifetime EP0466754B2 (fr) | 1989-04-06 | 1990-04-05 | Produit isolant en laine de fibre minerale, destine en particulier a l'isolation thermique de conduites et procede de preparation d'un tel produit |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0466754B2 (fr) |
JP (1) | JPH04506236A (fr) |
AT (1) | ATE124734T1 (fr) |
CA (1) | CA2051405A1 (fr) |
DE (1) | DE69020729T2 (fr) |
FI (1) | FI891659A (fr) |
RU (1) | RU2074147C1 (fr) |
WO (1) | WO1990012139A1 (fr) |
YU (1) | YU67090A (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR200103695T2 (tr) * | 1999-06-24 | 2002-05-21 | Paroc Group Oy Ab | Bir birleştirici maddenin imaline yönelik metod ve bunun kullanımı |
FI110261B (fi) † | 2000-06-20 | 2002-12-31 | Paroc Group Oy Ab | Menetelmä kolloidisen silikaattidispersion valmistamiseksi |
FI122457B (fi) * | 2006-09-21 | 2012-01-31 | Paroc Oy Ab | Menetelmä ja järjestelmä putkieristyskourun valmistamiseksi |
DE102008033447C5 (de) * | 2008-07-16 | 2020-03-05 | Hossein Maleki | Silikatische Baustoffmischung und deren Verwendungen |
EP2899072B1 (fr) * | 2014-01-24 | 2019-08-14 | BDD Beteiligungs GmbH | Dispositif d'isolation et son procédé de fabrication |
JP7021994B2 (ja) * | 2018-03-28 | 2022-02-17 | 太平洋マテリアル株式会社 | ロックウール組成物用結合材およびロックウール組成物 |
RU2691038C1 (ru) * | 2018-10-16 | 2019-06-07 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Вяжущее |
JP7232658B2 (ja) * | 2019-02-07 | 2023-03-03 | 太平洋マテリアル株式会社 | ロックウール組成物 |
JP7436172B2 (ja) * | 2019-09-25 | 2024-02-21 | 太平洋マテリアル株式会社 | 無機繊維成形体 |
EP4060105B1 (fr) * | 2021-02-26 | 2024-02-07 | Allshield Holding B.V. | Matériau non tissé durcissable à l'eau |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR798208A (fr) * | 1935-02-12 | 1936-05-12 | Isolants Union | Procédé pour l'obtention d'éléments isolants thermiques et phoniques |
CH238299A (de) * | 1944-01-21 | 1945-07-15 | Bruckmann Alex | Verfahren zur Herstellung eines isolierenden Überzuges auf heissen und kalten Flüssigkeitsleitungen aller Art sowie nach diesem Verfahren hergestellter Überzug. |
DK69522C (da) * | 1948-03-19 | 1949-07-04 | Herbert Edwards Krenchel | Fremgangsmåde til fremstilling af stive isolationsmaterialer. |
US2904444A (en) * | 1957-11-26 | 1959-09-15 | Fibreboard Paper Products Corp | Method of making calcareous-silicious insulating material |
GB1494280A (en) * | 1974-08-28 | 1977-12-07 | Proizv Tekhn Ob Rosorgtekhstro | Water glass compositions for the fabrication of thermal insulating materials |
DE2804069C2 (de) * | 1978-01-31 | 1986-02-27 | Bernd Dipl.-Chem. Dr. 6700 Ludwigshafen Steinkopf | Verfahren zur Herstellung von nicht-brennbaren Mineralfaserfilzen oder -platten |
-
1989
- 1989-04-06 FI FI891659A patent/FI891659A/fi not_active Application Discontinuation
-
1990
- 1990-04-05 DE DE69020729T patent/DE69020729T2/de not_active Expired - Fee Related
- 1990-04-05 CA CA002051405A patent/CA2051405A1/fr not_active Abandoned
- 1990-04-05 JP JP2505789A patent/JPH04506236A/ja active Pending
- 1990-04-05 YU YU00670/90A patent/YU67090A/xx unknown
- 1990-04-05 AT AT90905535T patent/ATE124734T1/de not_active IP Right Cessation
- 1990-04-05 RU SU905010086A patent/RU2074147C1/ru not_active IP Right Cessation
- 1990-04-05 EP EP90905535A patent/EP0466754B2/fr not_active Expired - Lifetime
- 1990-04-05 WO PCT/FI1990/000093 patent/WO1990012139A1/fr active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
FI891659A (fi) | 1990-10-07 |
CA2051405A1 (fr) | 1990-10-07 |
ATE124734T1 (de) | 1995-07-15 |
JPH04506236A (ja) | 1992-10-29 |
WO1990012139A1 (fr) | 1990-10-18 |
DE69020729D1 (de) | 1995-08-10 |
FI891659A0 (fi) | 1989-04-06 |
DE69020729T2 (de) | 1995-11-02 |
EP0466754A1 (fr) | 1992-01-22 |
RU2074147C1 (ru) | 1997-02-27 |
YU67090A (en) | 1991-08-31 |
EP0466754B2 (fr) | 2000-01-19 |
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